EP0413339A1 - Composite material for use in medicine - Google Patents
Composite material for use in medicine Download PDFInfo
- Publication number
- EP0413339A1 EP0413339A1 EP90115724A EP90115724A EP0413339A1 EP 0413339 A1 EP0413339 A1 EP 0413339A1 EP 90115724 A EP90115724 A EP 90115724A EP 90115724 A EP90115724 A EP 90115724A EP 0413339 A1 EP0413339 A1 EP 0413339A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composite material
- polymer
- material according
- dispersion
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000003814 drug Substances 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008093 supporting effect Effects 0.000 claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract 2
- 239000006185 dispersion Substances 0.000 claims description 30
- 235000015071 dressings Nutrition 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 239000004753 textile Substances 0.000 claims description 6
- 239000006261 foam material Substances 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004908 Emulsion polymer Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000000835 fiber Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000012876 carrier material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 8
- 208000027418 Wounds and injury Diseases 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920002689 polyvinyl acetate Polymers 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 208000010428 Muscle Weakness Diseases 0.000 description 2
- 206010028372 Muscular weakness Diseases 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940063559 methacrylic acid Drugs 0.000 description 2
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 2
- 230000000399 orthopedic effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 206010060820 Joint injury Diseases 0.000 description 1
- 206010061223 Ligament injury Diseases 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 208000029549 Muscle injury Diseases 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940063557 methacrylate Drugs 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 210000002787 omasum Anatomy 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/07—Stiffening bandages
- A61L15/12—Stiffening bandages containing macromolecular materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/233—Foamed or expanded material encased
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/237—Noninterengaged fibered material encased [e.g., mat, batt, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249982—With component specified as adhesive or bonding agent
Definitions
- the invention relates to a composite material for making supporting dressings or supporting structures for medical use, based on a porous carrier which is coated or impregnated with a polymer material capable of film formation.
- Supporting or reinforcing structures for use in various fields of medicine are in general in the form of bands, bandages and support materials or carrier materials. They are generally used for splinting bone fractures, for immobilizing injured joints and for support and immobilization in the case of ligament or muscle injuries. They can also be used for support in the case of muscular weakness or for correcting deformations.
- fabric bands which contain polyurethanes or form polyurethane-ureas and which crosslink after the application as a result of moisture, such as are described, for example, in DE 2,353,212.
- To initiate polymerization and curing previous immersion into water is necessary, which is frequently undesired by the user. Unduly high water temperatures here accelerate the polymerization reaction and, as a result, the quantity of energy released per unit time increases.
- This fact, and also putting on of too many plies, that is to say the so-called “oversizing" of such a dressing can in certain circumstances lead to skin burns on the patient. It is felt to be a further disadvantage that working with such a supporting dressing requires gloves.
- these bands must be manufactured with exclusion of moisture, in general in an environment having a relative humidity of less than 1%, and packaged in an air-tight and water-tight film of plastic/aluminum laminate or other completely tight packaging materials. Damaged or partially used packages are useless after a short time; only completely anhydrous fibers can be used as the carrier material. Toxicological problems due to free isocyanate can also not be com severelypletely excluded in manufacture and use.
- Another dressing material for making supporting dressings consists of a layer of a porous flexible material which is impregnated with a solution of a thermoplastic resin in a volatile organic solvent.
- This dressing material can be stored in a closed container and is solidified, after the dressing has been applied, by evaporation of the volatile solvent.
- bands which can be reactivated are also known from US Patent Specifications 2,218,710 and 3,649,319, wherein the gypsum normally used otherwise in supporting dressings has been replaced at least partially by polyvinyl acetate which, in the manufacture of the bands, is applied from an aqueous or alcoholic solution and then dried.
- these bands Before use as a supporting dressing, these bands must be immersed into water or moistened in another way and thus have the undesired disadvantages, described above, of bands which can be activated.
- the known dressing materials consisting of carrier materials and film-forming polymers must be reactivated before application either by heating or by impregnation with water and thus show the same disadvantages as the known gypsum dressings.
- dressing materials which are impregnated with a solution of a polymer in a volatile organic solvent, are admittedly ready for use immedi strictlyately, but toxic solvent vapors arise when they are used and, furthermore, the organic solvents are harmful to the skin.
- this object is achieved by means of a composite material for making supporting dressings or supporting structures for medical use, based on a porous flexible carrier which is coated or impregnated with polymer material capable of film formation, which is characterized in that the polymer material is in the form of an aqueous polymer dispersion, the polymer particles of which are capable of film formation on removal of water.
- the composite material according to the invention contains a porous carrier which is in the solid state of aggregation.
- porous is here to be understood as the property of a body to contain pores of any desired shape, namely the interstices between the fibers in textiles and other fibrous materials or the pores in a foam material.
- pores are generally understood as channels in a solid, starting at the surface of the latter, continuing into the interior thereof and, in some cases, penetrating right through it.
- absorbency is coupled to the property of porosity via the capillary action of the pores.
- a material is described as absorbent which is capable of absorbing a quite considerable quantity of fluid in itself and retaining it at least partially.
- those materials are preferred as carriers which, in addition to absorbency, also possess a certain flexibility, where flexible means that the material is at least approximately capable of adapting to given solid surfaces or is formable.
- web-shaped, band-shaped or fibrous materials are used, such as flat textile structures, in particular nonwovens and woven textiles and knitted textiles, bands and cords.
- natural or synthetic fibers are suitable.
- Suitable natural fibers can be of vegetable and/or animal origin. Vegetable fibers are understood both as vegetable fibers such as, for example, cotton and raffia fibers, for example flax, hemp and jute, as well as hard fibers, for example sisal.
- the animal fibers can be either wool, for example sheep's wool, or animal hair such as, for example, horsehair.
- chemical fibers of processed and/or regenerated natural and/or synthetic polymers can be used as the carrier material. These include both modified natural substances such as, for example, viscose and cellulose acetate, and protein fibers as well as purely synthetic fibers, for example polyester fibers, polyamide fibers and PVC fibers.
- Inorganic fibers for example mineral fibers, rock fibers, glass fibers, carbon fibers, metal fibers and/or slag fibers, can also be used as the carrier material.
- the carrier material which can be in the form of a band, nonwoven, cord and/or flat textile structure in woven and/or nonwoven form.
- foam materials or sponges above all of synthetic polymers, are particularly suitable as absorbent carriers.
- absorbent foam materials are known to a person skilled in the art, for example those based on polystyrene, polyvinyl chloride, polyethylene or polyurethane.
- the carrier described above is at least partially impregnated with an aqueous polymer dispersion.
- aqueous polymer dispersions which can be used within the scope of the invention, often described synonymously as a (polymer) emulsion, are known to those skilled in the art and are widely used as adhesives. Examples of suitable polymer dispersions are described in Ullmann, Enzyklopädie der ischen Chemie [Encyclopedia of Industrial Chemistry], volume 14, pages 241 and 242.
- Suitable polymer materials which are used according to the invention in the form of an aqueous dispersion for impregnating the carrier material, include homopolymers and/or copolymers of vinyl derivatives, such as vinyl esters, styrene, acrylic acid derivatives, methacrylic acid derivatives and organic polymers based on polyurethane, preferably polyurethane ionomers of the cationic and anionic type, in particular cationic ionomers based on polyurethane resins containing sulfonate groups and/or carboxyl groups.
- vinyl derivatives such as vinyl esters, styrene, acrylic acid derivatives, methmostacrylic acid derivatives and organic polymers based on polyurethane
- polyurethane ionomers of the cationic and anionic type in particular cationic ionomers based on polyurethane resins containing sulfonate groups and/or carboxyl groups.
- Suitable polymers of vinyl derivatives are homopolymers and copolymers of vinyl esters, such as of vinyl acetate, vinyl propionate and higher vinyl esters, such as vinyl laurate and vinyl esters of fatty acids. These monomers can be used by themselves or in the form of a mixture. Suitable comonomers for vinyl acetate and vinyl propionate are especially maleic acid esters, acrylic acid esters, ethylene, vinyl chloride, unsaturated carboxylic acids as well as higher vinyl esters such as vinyl laurate and vinyl esters of fatty acids. Polyvinyl acetate is particularly preferred.
- Emulsion polymers or dispersion polymers are, at least in part, preferred as the polymer material.
- the preparation of such polymers is known to those skilled in the art as emulsion polymerization.
- the process principles are explained, inter alia, in Ullmann (loc. cit.), volume 19, pages 132 et seq., and in Encyclopedia of Polymer Science and Engineering, volume 6, Wiley & Sons, New York 1986, pages 1-51. Methods based on this process and leading to polymer dispersions having novel, defined properties, have been described, for example, in DE 3,242,486 and DE 3,323,570.
- auxiliaries used for the emulsion polymerization are likewise known and can be divided essentially into initiators, emulsifiers and stabilizers or protective colloids. A wide range of these auxiliaries and a large number of different possible combinations are to be found in the literature.
- the polymer dispersions used according to the invention as impregnating agents have a solids content of 30% by weight to 80% by weight.
- Aqueous impregnating agents having a solids content of less than 30% by weight are disadvantageous, since an unduly high proportion of water entails disadvantages in application, such as, for example, long curing and drying times or dripping of the impregnating agent out of the carrier due to an unduly low viscosity.
- aqueous impregnating agents having a solids content greater than 80% by weight should not be used, in order to avoid, for example, a premature film formation during application.
- Preferred aqueous impregnating agents, which can be used within the scope of the invention have a solids content from 50% by weight to 75% by weight.
- auxiliaries contained in the composite material according to the invention, are known to those skilled in the art as auxiliaries for polymer dispersions, such as, for example, emulsifiers, antifoams, fillers, plasticizers, tackifiers, thickeners, solvents, pH regulators, coloring pigments, preservatives, complexing agents, anti-aging and anti-fatigue agents and/or the like.
- the impregnation of the carrier materials described with the likewise described impregnating agents can be carried out, for example, by immersing the carrier into the impregnating agent and subsequent dripping off after removal.
- Other types of application of the impregnating agent to the carrier are possible such as, for example, spreading, casting, spraying and blade-application.
- the impregnation can be effected, for example, by passing the band through a bath of impregnating agent and, if appropriate, subsequent squeezing by passing the impregnated band through the nip between two rollers running in opposite directions. If desired, such bands can subsequently be wound up into rolls.
- the solids content of the impregnating agent can be increased by suitable measures, known to those skilled in the art for water removal and/or by addition of redispersion powders, for example spray-dried synthetic resin dispersion, within the limits given according to the invention.
- the composite materials according to the invention do not yet show, in the state ready for use, any film formation and hence any tackiness.
- the film formation starts only when the residual water contained in the impregnating agent is removed.
- Film formation is understood as the coalescence and/or fusion of polymer particles to form a film.
- the minimum temperature at which this takes place is called the film formation temperature.
- the polymer dispersions used according to the invention as impregnating agents are chosen such that the film formation temperature, preferably the white point, is below the application temperature. A person skilled in the art understands the white point to be the minimim film formation temperature, at which the dispersion just no longer drys up to give a homogeneous clear film.
- the composite materials according to the invention for adhesive purposes can be used under application conditions which allow a removal of water, for example by evaporation.
- the film formation can be initiated, or at least promoted, by heating, aerating and/or addition of dehydrating agents.
- the composite materials according to the invention can readily be stored over a prolonged period, if they have been packaged at least largely in a water vapor-tight manner. Even partly used packages can readily be sealed again and stored at least for a limited time. Partial taking of the composite material in portions is thus possible. No special safety precautions are necessary in application.
- the application can take place in one working step, without preparatory measures and/or aftertreatment measures. However, measures known to a person skilled in the art, which promote evaporation or volatilization of the residual water, accelerate the film formation and shorten the drying time.
- Those formulations can be chosen in which, after the drying process, the composite material no longer shows any tackiness, at least at room temperature and below, and thus represents a reinforced, preferably fiber-reinforced plastic, in which the carrier material is now embedded in a solid plastic matrix.
- the hardness, the strength, stiffness or flexibility of the composite can be adjusted to defined requirements by suitable choice of the carrier, the polymer dispersions used and the auxiliaries such as, for example, plasticizers.
- "hard" dispersions such as, say, homopolymeric vinyl acetate, methacrylate or styrene dispersions, are selected.
- plasticizers incorporated in the polymer such as, for example, vinly laurate
- polymeric plasticizers such as, for example, soft resins or polyesters of aliphatic carboxylic acids
- monomeric plasticizers such as, for example, phthalates
- the composite material can be adjusted such that it is either waterproof or re-emulsifiable after the drying process.
- those synthetic resin dispersions can be used which allow crosslinking via the active groups, cf. Encyclopedia of Polymer Science and Engineering, J. Wiley & Sons, volume 8, pages 662 and 663, New York 1987, or via polydentate metal salts, as described in DE 3,434,668.
- the composite material according to the invention can advantageously be stored, in the state ready for use, in a sealed package which prevents evaporation of the water from the aqueous dispersion. In use, a part of the composite material or all the composite material can be taken from the package and used for the intended medical purpose.
- the composite material according to the invention is suitable for making rigid or flexible dressings, for immobilizing and fixing limbs and for making supporting dressings and supporting structures in the case of muscular weakness and joint injuries. It is also suitable for making orthopedic structures which are applied for correcting deformations.
- the composite material according to the invention can be used as a repair material for already existing supporting dressings and orthopedic structures, for example for repairs to prostheses.
- the composite material can also be layered in several superposed plies.
- aqueous polymer dispersions can in principle be used, such as are formed by means of conventional emulsion polymerization processes. Some of the examples given below are for such conventional polymerization processes.
- the reaction mixture was heated slowly to 75°C and, after the polymerization had started, a solution of 0.48 g of sodium bicarbonate was added.
- the batch was sized such that 289 ml of water in total were used. Within the next two hours, a further 261 g of vinyl acetate were added.
- the remainder of the potassium persulfate solution was added and the polymerization batch was heated at 90°C until visible reflux ceased. The dispersion was allowed to cool to 25°C, with slow stirring.
- Example 1 was repeated, but with the difference that a higher-molecular copolymer of acrylamide and N-tert.-butylacrylamide (K value 104) was used. A readily flowing and spreadable dispersion was obtained, which had a K value of 64.6 and a viscosity of 2,100 cP (Epprecht). In this dispersion again, no settling was observed on storage for more than 1 year.
- K value 104 a higher-molecular copolymer of acrylamide and N-tert.-butylacrylamide
- a homogeneous dispersion was obtained which showed excellent flow behavior and was soluble in dilute alkalis.
- the viscosity was 1,500 cP (Epprecht) and the K value was 61.
- the dispersion was stored for more than 1 year without a detrimental change being observed.
- Example 3 was repeated, but with the difference that 9 g of acrylamide/N-tert.-butylacrylamide copolymer were now used in place of 6 g thereof.
- a copolymer of 2-ethylhexyl acrylate, methyl methacrylate and a small proportion of methacrylic acid was prepared in the following way.
- the following emulsion was prepared in a stock vessel: 246.9 parts by weight of deionized water 1.5 parts by weight of C12/C14-fatty alcohol ether-sulfate (degree of ethoxylation 4) 5.00 parts by weight of nonionic emulsifier 1.9 parts by weight of peroxodisulfate 225.4 parts by weight of 2-ethylhexyl acrylate 254.8 parts by weight of methyl methacrylate 9.8 parts by weight of methacrylic acid.
- a solution of 0.24 part by weight of potassium peroxodisulfate and 9.56 parts by weight of deionized water was prepared in a dropping funnel.
- Feeding of the pre-emulsion into the reaction vessel was started at a temperature of 75°C, and the emulsion was added within about 2 hours by maintaining the exothermic reaction.
- the internal reaction temperature was 78 to 82°C.
- the solution of 0.24 part by weight of potassium peroxodisulfate in 4.56 parts by weight of deionized water, prepared in the dropping funnel, was then added for re-initiation.
- the reaction mixture was held for 60 minutes at temperatures between 85 and 90°C. After cooling to 30°C, the mixture was neutralized with a solution of 5 parts by weight of sodium hydrogen carbonate in 45 parts by weight of deionized water.
- the copolymer was obtained in the form of an aqueous dispersion.
- the vinyl aceate dispersion according to the invention was prepared as follows:
- composite materials according to the invention were prepared by impregnating various carrier materials with the aqueous polyvinyl acetate dispersion obtained according to Preparation Example 6.
- the coated or impregnated carrier materials were then squeezed by passing them through a nip located between two rollers rotating in opposite directions and wound up to a roll.
- a knitted glass fiber fabric of 7.5 cm width and a weight per unit area of 300 g/m2 was treated in the manner described above.
- the impregnating agent applied was 300 g/m2.
- a knitted polyester/cotton fabric of 1 cm width and a weight per unit area of 95 g/m2 was treated as described above.
- the impregnating agent applied was 250 g/m2.
- Test cylinders were wound in such a way that the individual plies are arranged congruently and flush one above the other.
- the internal diameter of the test cylinders was 75 mm in each case.
- the wound test cylinders are dried for 24 hours at 50°C and 30% relative humidity and then stored for one hour at room temperature (20°C).
- test cylinders were wound and dried.
- test cylinders wound and conditioned according to application example 3, from application examples 4 and 5 is determined by means of a universal testing machine (Franck).
- test cylinders are placed between a pair of pressure plates in such a way that the axis of the test cylinder is arranged parallel to the pressure plates.
- the testing force was determined which is required for deforming the test cylinder by 1 cm (testing speed 50 mm/minute). Results Application Example Number of plies in test cylinder Width of the test cylinders Force for 1 cm deformation 4 4 7.5 cm 228 N 5 8 11 cm 130 N 5 12 11 cm 310 N
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Abstract
Description
- The invention relates to a composite material for making supporting dressings or supporting structures for medical use, based on a porous carrier which is coated or impregnated with a polymer material capable of film formation.
- Supporting or reinforcing structures for use in various fields of medicine are in general in the form of bands, bandages and support materials or carrier materials. They are generally used for splinting bone fractures, for immobilizing injured joints and for support and immobilization in the case of ligament or muscle injuries. They can also be used for support in the case of muscular weakness or for correcting deformations.
- For the medical field, for making supporting dressings for the treatment of fractures, fabric bands are known which contain polyurethanes or form polyurethane-ureas and which crosslink after the application as a result of moisture, such as are described, for example, in DE 2,353,212. To initiate polymerization and curing, previous immersion into water is necessary, which is frequently undesired by the user. Unduly high water temperatures here accelerate the polymerization reaction and, as a result, the quantity of energy released per unit time increases. This fact, and also putting on of too many plies, that is to say the so-called "oversizing" of such a dressing, can in certain circumstances lead to skin burns on the patient. It is felt to be a further disadvantage that working with such a supporting dressing requires gloves. Moreover, these bands must be manufactured with exclusion of moisture, in general in an environment having a relative humidity of less than 1%, and packaged in an air-tight and water-tight film of plastic/aluminum laminate or other completely tight packaging materials. Damaged or partially used packages are useless after a short time; only completely anhydrous fibers can be used as the carrier material. Toxicological problems due to free isocyanate can also not be completely excluded in manufacture and use.
- Another dressing material, known from US Patent Specification 3,683,903, for making supporting dressings consists of a layer of a porous flexible material which is impregnated with a solution of a thermoplastic resin in a volatile organic solvent. This dressing material can be stored in a closed container and is solidified, after the dressing has been applied, by evaporation of the volatile solvent.
- For use as a supporting dressing in medicine, bands which can be reactivated are also known from US Patent Specifications 2,218,710 and 3,649,319, wherein the gypsum normally used otherwise in supporting dressings has been replaced at least partially by polyvinyl acetate which, in the manufacture of the bands, is applied from an aqueous or alcoholic solution and then dried. Before use as a supporting dressing, these bands must be immersed into water or moistened in another way and thus have the undesired disadvantages, described above, of bands which can be activated.
- The known dressing materials consisting of carrier materials and film-forming polymers must be reactivated before application either by heating or by impregnation with water and thus show the same disadvantages as the known gypsum dressings.
- On the other hand, dressing materials, which are impregnated with a solution of a polymer in a volatile organic solvent, are admittedly ready for use immediately, but toxic solvent vapors arise when they are used and, furthermore, the organic solvents are harmful to the skin.
- It is thus the object of the invention to provide a composite material which is suitable for making supporting dressings and supporting structures for medical use and which can be stored and handled without problems, is solvent-free and toxicologically acceptable, adapts easily to the limbs to be supported, and after curing, shows favorable properties, such as increased strength and light weight.
- According to the invention, this object is achieved by means of a composite material for making supporting dressings or supporting structures for medical use, based on a porous flexible carrier which is coated or impregnated with polymer material capable of film formation, which is characterized in that the polymer material is in the form of an aqueous polymer dispersion, the polymer particles of which are capable of film formation on removal of water.
- The composite material according to the invention contains a porous carrier which is in the solid state of aggregation. The term porous is here to be understood as the property of a body to contain pores of any desired shape, namely the interstices between the fibers in textiles and other fibrous materials or the pores in a foam material.
- In foam materials or cured foams, the volumes not filled by the solid are described as pores, a distinction being made between open pores and closed pores. Open pores are generally understood as channels in a solid, starting at the surface of the latter, continuing into the interior thereof and, in some cases, penetrating right through it.
- Frequently, the property of absorbency is coupled to the property of porosity via the capillary action of the pores. A material is described as absorbent which is capable of absorbing a quite considerable quantity of fluid in itself and retaining it at least partially.
- Within the scope of the invention, those materials are preferred as carriers which, in addition to absorbency, also possess a certain flexibility, where flexible means that the material is at least approximately capable of adapting to given solid surfaces or is formable. Preferably, web-shaped, band-shaped or fibrous materials are used, such as flat textile structures, in particular nonwovens and woven textiles and knitted textiles, bands and cords.
- For making the carrier material, natural or synthetic fibers are suitable. Suitable natural fibers can be of vegetable and/or animal origin. Vegetable fibers are understood both as vegetable fibers such as, for example, cotton and raffia fibers, for example flax, hemp and jute, as well as hard fibers, for example sisal. The animal fibers can be either wool, for example sheep's wool, or animal hair such as, for example, horsehair. Moreover, chemical fibers of processed and/or regenerated natural and/or synthetic polymers can be used as the carrier material. These include both modified natural substances such as, for example, viscose and cellulose acetate, and protein fibers as well as purely synthetic fibers, for example polyester fibers, polyamide fibers and PVC fibers.
- Inorganic fibers, for example mineral fibers, rock fibers, glass fibers, carbon fibers, metal fibers and/or slag fibers, can also be used as the carrier material.
- Furthermore, any combination of the abovementioned fiber types is possible as the carrier material, which can be in the form of a band, nonwoven, cord and/or flat textile structure in woven and/or nonwoven form.
- Moreover, foam materials or sponges, above all of synthetic polymers, are particularly suitable as absorbent carriers. Such absorbent foam materials are known to a person skilled in the art, for example those based on polystyrene, polyvinyl chloride, polyethylene or polyurethane.
- According to the invention, the carrier described above is at least partially impregnated with an aqueous polymer dispersion. The aqueous polymer dispersions, which can be used within the scope of the invention, often described synonymously as a (polymer) emulsion, are known to those skilled in the art and are widely used as adhesives. Examples of suitable polymer dispersions are described in Ullmann, Enzyklopädie der technischen Chemie [Encyclopedia of Industrial Chemistry], volume 14, pages 241 and 242.
- Suitable polymer materials which are used according to the invention in the form of an aqueous dispersion for impregnating the carrier material, include homopolymers and/or copolymers of vinyl derivatives, such as vinyl esters, styrene, acrylic acid derivatives, methacrylic acid derivatives and organic polymers based on polyurethane, preferably polyurethane ionomers of the cationic and anionic type, in particular cationic ionomers based on polyurethane resins containing sulfonate groups and/or carboxyl groups.
- Suitable polymers of vinyl derivatives are homopolymers and copolymers of vinyl esters, such as of vinyl acetate, vinyl propionate and higher vinyl esters, such as vinyl laurate and vinyl esters of fatty acids. These monomers can be used by themselves or in the form of a mixture. Suitable comonomers for vinyl acetate and vinyl propionate are especially maleic acid esters, acrylic acid esters, ethylene, vinyl chloride, unsaturated carboxylic acids as well as higher vinyl esters such as vinyl laurate and vinyl esters of fatty acids. Polyvinyl acetate is particularly preferred.
- Polyvinyl acetate dispersions have been described, for example in US Patent Specification 1,084,581.
- Emulsion polymers or dispersion polymers are, at least in part, preferred as the polymer material. The preparation of such polymers is known to those skilled in the art as emulsion polymerization. The process principles are explained, inter alia, in Ullmann (loc. cit.), volume 19, pages 132 et seq., and in Encyclopedia of Polymer Science and Engineering, volume 6, Wiley & Sons, New York 1986, pages 1-51. Methods based on this process and leading to polymer dispersions having novel, defined properties, have been described, for example, in DE 3,242,486 and DE 3,323,570.
- The auxiliaries used for the emulsion polymerization are likewise known and can be divided essentially into initiators, emulsifiers and stabilizers or protective colloids. A wide range of these auxiliaries and a large number of different possible combinations are to be found in the literature.
- The polymer dispersions used according to the invention as impregnating agents have a solids content of 30% by weight to 80% by weight. Aqueous impregnating agents having a solids content of less than 30% by weight are disadvantageous, since an unduly high proportion of water entails disadvantages in application, such as, for example, long curing and drying times or dripping of the impregnating agent out of the carrier due to an unduly low viscosity. On the other hand, aqueous impregnating agents having a solids content greater than 80% by weight should not be used, in order to avoid, for example, a premature film formation during application. Preferred aqueous impregnating agents, which can be used within the scope of the invention, have a solids content from 50% by weight to 75% by weight.
- The desired auxiliaries, contained in the composite material according to the invention, are known to those skilled in the art as auxiliaries for polymer dispersions, such as, for example, emulsifiers, antifoams, fillers, plasticizers, tackifiers, thickeners, solvents, pH regulators, coloring pigments, preservatives, complexing agents, anti-aging and anti-fatigue agents and/or the like.
- The impregnation of the carrier materials described with the likewise described impregnating agents can be carried out, for example, by immersing the carrier into the impregnating agent and subsequent dripping off after removal. Other types of application of the impregnating agent to the carrier are possible such as, for example, spreading, casting, spraying and blade-application. In the case of carriers in the form of bands, the impregnation can be effected, for example, by passing the band through a bath of impregnating agent and, if appropriate, subsequent squeezing by passing the impregnated band through the nip between two rollers running in opposite directions. If desired, such bands can subsequently be wound up into rolls. If appropriate, the solids content of the impregnating agent can be increased by suitable measures, known to those skilled in the art for water removal and/or by addition of redispersion powders, for example spray-dried synthetic resin dispersion, within the limits given according to the invention.
- Because of the impregnating agents used according to the invention, the composite materials according to the invention do not yet show, in the state ready for use, any film formation and hence any tackiness. The film formation starts only when the residual water contained in the impregnating agent is removed. Film formation is understood as the coalescence and/or fusion of polymer particles to form a film. The minimum temperature at which this takes place is called the film formation temperature. The polymer dispersions used according to the invention as impregnating agents are chosen such that the film formation temperature, preferably the white point, is below the application temperature. A person skilled in the art understands the white point to be the minimim film formation temperature, at which the dispersion just no longer drys up to give a homogeneous clear film. The composite materials according to the invention for adhesive purposes can be used under application conditions which allow a removal of water, for example by evaporation. The film formation can be initiated, or at least promoted, by heating, aerating and/or addition of dehydrating agents.
- In the state ready for use, the composite materials according to the invention can readily be stored over a prolonged period, if they have been packaged at least largely in a water vapor-tight manner. Even partly used packages can readily be sealed again and stored at least for a limited time. Partial taking of the composite material in portions is thus possible. No special safety precautions are necessary in application. The application can take place in one working step, without preparatory measures and/or aftertreatment measures. However, measures known to a person skilled in the art, which promote evaporation or volatilization of the residual water, accelerate the film formation and shorten the drying time.
- Those formulations can be chosen in which, after the drying process, the composite material no longer shows any tackiness, at least at room temperature and below, and thus represents a reinforced, preferably fiber-reinforced plastic, in which the carrier material is now embedded in a solid plastic matrix. The hardness, the strength, stiffness or flexibility of the composite can be adjusted to defined requirements by suitable choice of the carrier, the polymer dispersions used and the auxiliaries such as, for example, plasticizers. For such supporting composites, for example "hard" dispersions, such as, say, homopolymeric vinyl acetate, methacrylate or styrene dispersions, are selected. As a shortened list of examples of known plasticizers, plasticizers incorporated in the polymer, such as, for example, vinly laurate, polymeric plasticizers such as, for example, soft resins or polyesters of aliphatic carboxylic acids, and monomeric plasticizers such as, for example, phthalates may be mentioned.
- By an appropriate selection of the dispersion or additives, the composite material can be adjusted such that it is either waterproof or re-emulsifiable after the drying process. For composite materials which are to be waterproof after drying, those synthetic resin dispersions can be used which allow crosslinking via the active groups, cf. Encyclopedia of Polymer Science and Engineering, J. Wiley & Sons, volume 8, pages 662 and 663, New York 1987, or via polydentate metal salts, as described in DE 3,434,668.
- The composite material according to the invention can advantageously be stored, in the state ready for use, in a sealed package which prevents evaporation of the water from the aqueous dispersion. In use, a part of the composite material or all the composite material can be taken from the package and used for the intended medical purpose. The composite material according to the invention is suitable for making rigid or flexible dressings, for immobilizing and fixing limbs and for making supporting dressings and supporting structures in the case of muscular weakness and joint injuries. It is also suitable for making orthopedic structures which are applied for correcting deformations.
- Furthermore, the composite material according to the invention can be used as a repair material for already existing supporting dressings and orthopedic structures, for example for repairs to prostheses.
- In all the abovementioned applications, the composite material can also be layered in several superposed plies.
- For producing the composite materials according to the invention, aqueous polymer dispersions can in principle be used, such as are formed by means of conventional emulsion polymerization processes. Some of the examples given below are for such conventional polymerization processes.
- 6 g of a copolymer of acrylamide and N-tert.-butylacrylamide in 1:1 weight ratio, dissolved in 180 ml of water, as a protective colloid and 12 g of a 10% solution of an acidic phosphoric acid ester of a fatty alcohol/ethylene oxide adduct as an emulsifier and 0.69.g of sodium laurylsulfate were placed into a flask provided with stirrer, reflux condenser, thermometer and gas inlet tube. Under a nitrogen atmosphere, 30 g of vinyl acetate and then 80% of an aqueous solution of 0.9 g of potassium persulfate and a solution of 0.06 g of sodium sulfite in water were added. The reaction mixture was heated slowly to 75°C and, after the polymerization had started, a solution of 0.48 g of sodium bicarbonate was added. The batch was sized such that 289 ml of water in total were used. Within the next two hours, a further 261 g of vinyl acetate were added. After the polymerization was substantially complete, the remainder of the potassium persulfate solution was added and the polymerization batch was heated at 90°C until visible reflux ceased. The dispersion was allowed to cool to 25°C, with slow stirring.
- A readily flowing, homogeneous dispersion having a viscosity of 900 cP (according to Epprecht) and a K value of 59 was obtained.
- Example 1 was repeated, but with the difference that a higher-molecular copolymer of acrylamide and N-tert.-butylacrylamide (K value 104) was used. A readily flowing and spreadable dispersion was obtained, which had a K value of 64.6 and a viscosity of 2,100 cP (Epprecht). In this dispersion again, no settling was observed on storage for more than 1 year.
- In the manner described in the preceding examples, the copolymerization of 279 g of vinyl acetate and 9.6 g of crotonic acid was carried out, using 284 cm³ of water in total. However, the following quantities of protective colloid and emulsifier were used:
6.0 g of acrylamide/N-tert.-butylacrylamide copolymer (K value 98, 1:1 weight ratio);
18.0 g of a 10% solution of the phosphated ethylene oxide addition products to coconut fatty alcohol;
1.4 g of lauryl sulfate. - A homogeneous dispersion was obtained which showed excellent flow behavior and was soluble in dilute alkalis. The viscosity was 1,500 cP (Epprecht) and the K value was 61.
- The dispersion was stored for more than 1 year without a detrimental change being observed.
- Example 3 was repeated, but with the difference that 9 g of acrylamide/N-tert.-butylacrylamide copolymer were now used in place of 6 g thereof.
- A readily spreadable, alkali-soluble dispersion having a viscosity of 3,400 cP (Epprecht) was obtained, which was still unchanged after storage for more than 1 year.
- A copolymer of 2-ethylhexyl acrylate, methyl methacrylate and a small proportion of methacrylic acid was prepared in the following way.
- 195.64 parts by weight of deionized water
3.50 parts by weight of C₁₂/₁₄,-fatty alcohol ether-sulfate (degree of ethoxylation 4); 100% of active substance
0.24 part by weight of potassium peroxodisulfate
0.5 part by weight of sodium hydrogen carbonate
were placed into a reactor. The latter was flushed with nitrogen for 20 minutes and then heated to 75°C. - Separately therefrom, the following emulsion was prepared in a stock vessel:
246.9 parts by weight of deionized water
1.5 parts by weight of C₁₂/C₁₄-fatty alcohol ether-sulfate (degree of ethoxylation 4)
5.00 parts by weight of nonionic emulsifier
1.9 parts by weight of peroxodisulfate
225.4 parts by weight of 2-ethylhexyl acrylate
254.8 parts by weight of methyl methacrylate
9.8 parts by weight of methacrylic acid.
A solution of 0.24 part by weight of potassium peroxodisulfate and 9.56 parts by weight of deionized water was prepared in a dropping funnel. - Feeding of the pre-emulsion into the reaction vessel was started at a temperature of 75°C, and the emulsion was added within about 2 hours by maintaining the exothermic reaction. The internal reaction temperature was 78 to 82°C. The solution of 0.24 part by weight of potassium peroxodisulfate in 4.56 parts by weight of deionized water, prepared in the dropping funnel, was then added for re-initiation. For this purpose, the reaction mixture was held for 60 minutes at temperatures between 85 and 90°C. After cooling to 30°C, the mixture was neutralized with a solution of 5 parts by weight of sodium hydrogen carbonate in 45 parts by weight of deionized water.
- The copolymer was obtained in the form of an aqueous dispersion.
- The vinyl aceate dispersion according to the invention was prepared as follows:
- 3 kg of a commercially available aqueous dispersion of vinyl acetate homopolymer with polyvinyl alcohol as the protective colloid and a solids content of 65% by weight is first introduced into a beaker. With fast stirring, 750 g of commercially available homopolyvinyl acetate redispersion powder were slowly added. The powder was here added in stages, that is to say the addition was interrupted several times, the stirrer was turned off and the system was given an opportunity for "degassing", that is to say allowing air which had been stirred in to escape again. After complete addition of the powder, the dispersion, which can be used according to the invention, had a solids content of 72% by weight.
- In the application examples which follow, composite materials according to the invention were prepared by impregnating various carrier materials with the aqueous polyvinyl acetate dispersion obtained according to Preparation Example 6. The coated or impregnated carrier materials were then squeezed by passing them through a nip located between two rollers rotating in opposite directions and wound up to a roll.
- The rolls thus produced were packaged in sealable polyethylene bags.
- A knitted glass fiber fabric of 7.5 cm width and a weight per unit area of 300 g/m² was treated in the manner described above. The impregnating agent applied was 300 g/m².
- A knitted polyester/cotton fabric of 1 cm width and a weight per unit area of 95 g/m² was treated as described above. The impregnating agent applied was 250 g/m².
- Test cylinders were wound in such a way that the individual plies are arranged congruently and flush one above the other. The internal diameter of the test cylinders was 75 mm in each case. To determine the stability, the wound test cylinders are dried for 24 hours at 50°C and 30% relative humidity and then stored for one hour at room temperature (20°C).
- In this way, the following test cylinders were wound and dried.
- Four-ply test cylinder from application Example 1.
- 8-Ply and 12-ply test cylinders from Application Example 2 were wound.
- The stability of the test cylinders, wound and conditioned according to application example 3, from application examples 4 and 5 is determined by means of a universal testing machine (Franck).
- The test cylinders are placed between a pair of pressure plates in such a way that the axis of the test cylinder is arranged parallel to the pressure plates. The testing force was determined which is required for deforming the test cylinder by 1 cm (testing speed 50 mm/minute).
Results Application Example Number of plies in test cylinder Width of the test cylinders Force for 1 cm deformation 4 4 7.5 cm 228 N 5 8 11 cm 130 N 5 12 11 cm 310 N - The above test results show that the supporting dressings according to the invention have excellent strength after drying.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3927030A DE3927030A1 (en) | 1989-08-16 | 1989-08-16 | COMPOSITE FOR USE IN MEDICINE |
DE3927030 | 1989-08-16 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0413339A1 true EP0413339A1 (en) | 1991-02-20 |
EP0413339B1 EP0413339B1 (en) | 1993-01-27 |
Family
ID=6387216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90115724A Expired - Lifetime EP0413339B1 (en) | 1989-08-16 | 1990-08-16 | Composite material for use in medicine |
Country Status (8)
Country | Link |
---|---|
US (1) | US5169698A (en) |
EP (1) | EP0413339B1 (en) |
JP (1) | JP2983043B2 (en) |
CA (1) | CA2023152C (en) |
DE (2) | DE3927030A1 (en) |
ES (1) | ES2038024T3 (en) |
GR (1) | GR1000689B (en) |
IE (1) | IE64432B1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994005339A1 (en) * | 1992-09-07 | 1994-03-17 | Universite De Liege | Combinations in composite form of flexible or rigid materials which are formable and adhesive at temperatures below 90 °c |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5382445A (en) * | 1993-01-25 | 1995-01-17 | Minnesota Mining And Manufacturing Company | Mechanically compacted fabrics for orthopedic casting tapes |
US5405643A (en) * | 1993-01-25 | 1995-04-11 | Minnesota Mining And Manufacturing Company | Microcreping of fabrics for orthopedic casting tapes |
US5455060A (en) * | 1993-10-25 | 1995-10-03 | Minnesota Mining And Manufacturing Company | Compacted fabrics for orthopedic casting tapes |
US5370927A (en) * | 1993-10-25 | 1994-12-06 | Minnesota Mining And Manufacturing Company | Wet compacting of fabrics for orthopedic casting tapes |
CA2117875A1 (en) * | 1993-10-25 | 1995-04-26 | James C. Novack | Vibration compacted fabrics for orthopedic casting tape |
DE19754560A1 (en) * | 1997-12-09 | 1999-06-10 | Wws Ideen Aus Pu Gmbh | Orthopedic device for supporting e.g. knee, elbow joint |
US6231533B1 (en) | 1999-05-21 | 2001-05-15 | Ppg Industries Ohio, Inc. | Orthopedic splinting article |
DE10139891C1 (en) * | 2001-08-20 | 2002-12-19 | Spig Schutzplanken Prod Gmbh | Steel crash barrier for motorway has coupling housing at ends of abutting crash barrier sections for coupling together by insertion of vertical coupling pins |
DE10157286C1 (en) * | 2001-11-22 | 2003-05-08 | Lafarge Roofing Components | Material for fixing ridge tiles on roof tiles comprises filter foam impregnated with liquid which cures to fix tiles together |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE8624190U1 (en) * | 1986-09-05 | 1986-12-04 | Karl Otto Braun Kg, 6759 Wolfstein | COHESIVE FABRIC |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2697434A (en) * | 1952-07-19 | 1954-12-21 | Du Pont | Surgical cast and process of forming it |
GB1176161A (en) * | 1966-04-06 | 1970-01-01 | Dunlop Co Ltd | Method for the Manufacture of Flexible Sheet Materials |
US3649436A (en) * | 1970-05-22 | 1972-03-14 | Johnson & Johnson | Cohesive sheet |
DE3410169A1 (en) * | 1984-03-20 | 1985-09-26 | Karl Otto Braun Kg, 6759 Wolfstein | Process for producing a cohesive bandage for immovable dressings, compression dressings and suspensory dressings and bandage produced according to this process |
DE3605198A1 (en) * | 1986-02-19 | 1987-08-20 | Bayer Ag | LAMINATE BANDAGE |
-
1989
- 1989-08-16 DE DE3927030A patent/DE3927030A1/en active Granted
-
1990
- 1990-08-13 CA CA002023152A patent/CA2023152C/en not_active Expired - Lifetime
- 1990-08-15 IE IE296390A patent/IE64432B1/en not_active IP Right Cessation
- 1990-08-16 DE DE9090115724T patent/DE69000820T2/en not_active Expired - Fee Related
- 1990-08-16 ES ES199090115724T patent/ES2038024T3/en not_active Expired - Lifetime
- 1990-08-16 JP JP2216446A patent/JP2983043B2/en not_active Expired - Fee Related
- 1990-08-16 GR GR900100618A patent/GR1000689B/en not_active IP Right Cessation
- 1990-08-16 EP EP90115724A patent/EP0413339B1/en not_active Expired - Lifetime
- 1990-10-11 US US07/596,832 patent/US5169698A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE8624190U1 (en) * | 1986-09-05 | 1986-12-04 | Karl Otto Braun Kg, 6759 Wolfstein | COHESIVE FABRIC |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994005339A1 (en) * | 1992-09-07 | 1994-03-17 | Universite De Liege | Combinations in composite form of flexible or rigid materials which are formable and adhesive at temperatures below 90 °c |
BE1006172A3 (en) * | 1992-09-07 | 1994-05-31 | Liegeois Jean Marie | Combination in the form of composite materials, or flexible rigid or adhesives moldable under the influence of a lower temperature 90 degrees c. |
US5536544A (en) * | 1992-09-07 | 1996-07-16 | Liegeois; Jean M. | Flexible or rigid combinations of materials in composite form which are formable and adhesive at temperatures below 90° C. |
Also Published As
Publication number | Publication date |
---|---|
DE69000820D1 (en) | 1993-03-11 |
EP0413339B1 (en) | 1993-01-27 |
JP2983043B2 (en) | 1999-11-29 |
ES2038024T3 (en) | 1993-07-01 |
US5169698A (en) | 1992-12-08 |
IE64432B1 (en) | 1995-08-09 |
JPH03178663A (en) | 1991-08-02 |
DE69000820T2 (en) | 1993-08-19 |
GR1000689B (en) | 1992-10-08 |
GR900100618A (en) | 1991-12-30 |
DE3927030C2 (en) | 1992-07-16 |
DE3927030A1 (en) | 1991-02-21 |
IE902963A1 (en) | 1991-02-27 |
CA2023152C (en) | 1994-10-04 |
CA2023152A1 (en) | 1991-02-17 |
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